Perfluoropolyether silanes and use thereof

ABSTRACT

The present invention provides novel perfluoropolyether silanes, compositions containing the novel perfluoropolyether silanes and method of treating substrates, in particular substrates having a hard surface such as ceramics or glass, to render them water, oil, stain, and/or dirt repellent.

FIELD OF THE INVENTION

The present invention relates to novel perfluoropolyether silanes,compositions containing the novel perfluoropolyether silanes and methodof treating substrates, in particular substrates having a hard surfacesuch as ceramics or glass, to render them water, oil, stain, and/or dirtrepellent. The present invention also relates to compositions for use insuch a method.

BACKGROUND OF THE INVENTION

The use of fluorinated silanes, i.e., silane compounds that have one ormore fluorinated groups for rendering substrates such as glass andceramics oil and water repellent are known. For example U.S. Pat. No.5,274,159 describes destructible fluorinated alkoxy silane surfactantsthat can be applied from an aqueous solution. WO 02/30848 describescompositions comprising fluorinated polyether silanes for renderingceramics oil and water repellent.

EP 797111 discloses compositions of alkoxysilane compounds containingperfluoropolyether groups to form antifouling layers on opticalcomponents. Additionally, U.S. Pat. No. 6,200,884 discloses compositionsof perfluoropolyether-modified aminosilanes that cure into films havingimproved water and oil repellency and anti-stain properties.

EP 789050 discloses the use of fluorinated polyether silanes for makingcomposite film coatings. U.S. Pat. No. 3,646,085 teaches fluorinatedpolyether silanes for rendering glass or metal surfaces oil and waterrepellent. WO 99/37720 discloses fluorinated polyether silanes forproviding antisoiling coating to antireflective surfaces on substratessuch as glass or plastic. U.S. Pat. No. 3,950,588 discloses the use offluorinated polyether silanes to render ceramic surfaces such asbathroom tiles or cookware water and/or oil repellent.

SUMMARY OF THE INVENTION

The present invention provides novel perfluoropolyether silanes of theformula:R_(f)[—R¹—C₂H₄—S—R²—Si(Y)_(x)(R³)_(3-x)]_(y),wherein

-   -   R_(f) is a mono- or divalent perfluoropolyether group,    -   R¹ is a covalent bond, —O—, or a divalent alkylene or arylene        group, or combinations thereof, said alkylene groups optionally        containing one or more catenary oxygen atoms;    -   R² is a divalent alkylene or arylene group, or combinations        thereof, said alkylene groups optionally containing one or more        catenary oxygen atoms;    -   Y is a hydrolysable group, and    -   R³ is a monovalent alkyl or aryl group, x is 1, 2 or 3,        preferably 3, and    -   y is 1 or 2.

Although many fluorinated silane compositions are known in the art fortreating substrates to render them oil and water repellent, therecontinues to be a desire to provide further improved compositions forthe treatment of substrates, in particular substrates having a hardsurface such as ceramics, glass and stone, in order to render them waterand oil repellent and easy to clean.

There is also a need for treating glass and plastic as a hard surface,particularly in the ophthalmic field, in order to render themantisoiling, i.e. stain, dirt, oil and/or water resistant. Desirably,such compositions and methods employing them can yield coatings thathave improved properties. In particular, it would be desirable toimprove the durability of the coating, including an improved abrasionresistance of the coating. Furthermore, improving the ease of cleaningof such substrates while using less detergents, water or manual labor,is not only a desire by the end consumer, but has also a positive impacton the environment. The compositions can conveniently be applied in aneasy and safe way and are compatible with existing manufacturingmethods. Preferably, the compositions will fit easily into themanufacturing processes that are practiced to produce the substrates tobe treated. The compositions preferably also avoid the use ofecologically objectionable components.

The present invention further provides a method for coating a substrate,particularly a hard substrate, with the perfluoropolyether silanes toprovide an antisoiling coating thereto. In one embodiment, the presentinvention provides a method of depositing the perfluoropolyether silaneson a substrate comprising vaporizing the perfluoropolyether silane anddepositing it onto a substrate, such as by vapor deposition techniques.In another embodiment, the invention comprises a coating compositioncomprising the perfluoropolyether silane and a solvent, whereby thecoating compositions are applied to substrates to impart an antisoilingcoating thereto.

DETAILED DESCRIPTION

The present invention provides novel perfluoropolyether silanes, andsubstrates bearing a coating of the perfluoropolyether silanes. Thesilanes are of the formulaR_(f)[—R¹—C₂H₄—S—R²—Si(Y)_(x)(R³)_(3-x)]_(y),wherein

-   -   R_(f) is a mono- or divalent perfluoropolyether group,    -   R¹ is a covalent bond, —O—, or a divalent alkylene or arylene        group, or combinations thereof, said alkylene groups optionally        containing one or more catenary (in-chain) oxygen atoms;    -   R² is a divalent alkylene or arylene groups, or combinations        thereof, said alkylene groups optionally containing one or more        catenary oxygen atoms;    -   Y is a hydrolysable group, and    -   R³ is a monovalent alkyl or aryl group, x is 1, 2 or 3,        preferably 3, and    -   y is 1 or 2.

R_(f) represents a mono- or divalent perfluoropolyether group. Theperfluoropolyether group can include linear, branched, and/or cyclicstructures, and may be saturated or unsaturated. It is a perfluorinatedgroup, i.e., essentially all C—H bonds are replaced by C—F bonds.Preferably, it includes perfluorinated repeating units selected from thegroup of —(C_(n)F_(2n))—, —(C_(n)F_(2n)O)—, —(CF(Z))—, —(CF(Z)O)—,—(CF(Z)C_(n)F_(2n)O)—, —(C_(n)F_(2n)CF(Z)O)—, —(CF₂CF(Z)O)—, andcombinations thereof. In these repeating units Z is a perfluoroalkylgroup, a perfluoroalkoxy group, or perfluoroether group, all of whichcan be linear, branched, or cyclic, and preferably have about 1 to about9 carbon atoms and 0 to about 4 oxygen atoms. “n” is at least 1, andpreferably 1 to 4. Examples of perfluoropolyethers containing theserepeating units are disclosed in U.S. Pat. No. 5,306,758 (Pellerite).

For the monovalent perfluoropolyether group (wherein y is 1 in formula(I) above), the terminal groups can be (C_(n)F_(2n+1))—,(C_(n)F_(2n+1)O)— or (X′C_(n)F_(2n)O)—, which may be linear or branchedand wherein X′ is H, Cl, or Br, for example. Preferably, these terminalgroups are perfluorinated. In these repeating units or terminal groups,n is 1 or more, and preferably 1 to 8. Preferred approximate averagestructures for a divalent fluorinated polyether group include —C₄F₈O—,C₃—F₆O—, —C₅F₁₀O—, —C₆F₁₂O—, —CF₂O(CF₂O)_(m)(C₂F₄O)_(p)CF₂—, wherein anaverage value for m and p is 0 to 50, with the proviso that m and p arenot simultaneously 0, —CF₂O(C₂F₄O)_(p)CF₂—,—CF(CF₃)O—(CF₂CF(CF₃)O)_(p)—C₄F₈O—(CF(CF₃)CF₂O)_(p)—CF(CF₃)—, and—(CF₂)₃O(C₄F₈O)_(p)(CF₂)₃—, wherein an average value for each p is 1 to50.

Of these, particularly preferred approximate average structures are—CF₂O(CF₂O)_(m)(C₂F₄O)_(p)CF₂—, —CF₂O(C₂F₄O)_(p)CF₂—, and—CF(CF₃)O—(CF₂CF(CF₃)O)_(p)—C₄F₈O—(CF(CF₃)CF₂O)_(p)—CF(CF₃)—.Particularly preferred approximate average structures for a monovalentperfluoropolyether group include C₃F₇O(CF(CF₃)CF₂O)_(p)CF(CF₃)— andCF₃O(C₂F₄O)_(p)CF₂— wherein an average value for p is 1 to 50. Assynthesized, these compounds typically include a mixture of polymers.

The divalent R¹ and R² groups can independently include linear,branched, or cyclic structures that may be saturated or unsaturated,including alkylene, arylene and combinations thereof, such as aralkyleneand alkarylene. The R¹ and R² groups can contain one or more catenaryheteroatoms (e.g., oxygen, nitrogen, or sulfur). The groups can also besubstituted with halogen atoms, preferably, fluorine atoms, althoughthis is less desirable, as this might lead to instability of thecompound.

Preferably, the R¹ and R² groups are hydrocarbon groups, preferably,linear hydrocarbon groups, optionally containing one or more catenaryheteroatoms. Examples of R¹ and R² groups include alkylenes of theformula —(C_(m)H_(2m))—, wherein m is about 2 to about 20, and one ormore non-adjacent —CH₂— groups are replaced by ether oxygen atoms, e.g.—(C_(m)H_(2m))—O—(C_(m′)H_(2m′))—, where m is 2 to 20, m′ is 0 to 20 andm+m′ is 2 to 20.

Y represents a hydrolysable group in formula (I) such as for example ahalide, a C₁-C₄ alkoxy group, an acyloxy group or a polyoxyalkylenegroup, such as polyoxyethylene groups as disclosed in U.S. Pat. No.5,274,159. By hydrolysable it is meant the Y group will undergo anexchange reaction with water to form a Si—OH moiety, which may furtherreact to form siloxane groups. Specific examples of hydrolysable groupsinclude methoxy, ethoxy and propoxy groups, chlorine and an acetoxygroup.

R³ is a monovalent alkyl or aryl group and is generallynon-hydrolyzable.

Compounds of formula I suitable for compositions for treating substratesof the present invention have a molecular weight (number average) of atleast about 200, and preferably, at least about 1000. Preferably, theyare no greater than about 10000.

Examples of preferred perfluoropolyether silanes include, but are notlimited to, the following approximate average structures. The number ofrepeat units n and m will vary, with n from 1 to 50, generally 3 to 30,and n+m up to 30.

-   C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂OC₃H₆SC₃H₆Si(OCH₃)₃-   C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂OC₃H₆SC₃H₆Si(OC₂H₅)₂-   C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CO₂C₃H₆SC₃H₆Si(OCH₃)₃-   C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CO₂C₃H₆SC₃H₆Si(OC₂H₅)₃-   (CH₃O)₃SiC₃H₆SC₃H₆OCH₂CF₂(OC₂F₄)_(n)(OCF₂)_(n)CF₂CH₂OC₃H₆SC₃H₆Si(OCH₃)₃-   (C₂H₅O)₃SiC₃H₆SC₃H₆OCH₂CF₂(OC₂F₄)_(n)(OCF₂)_(n)CF₂CH₂OC₃H₆SC₃H₆Si(OC₂H₅)₃-   (CH₃O)₃SiC₃H₆SC₃H₆OCH₂CF(CF₃)[OCF₂CF(CF₃)]_(n)OC₄F₉O[(CF(CF₃)CF₂O]_(m)CF(CF₃)CH₂OC₃H₆SC₃H₆Si(OCH₃)₃-   (C₂H₅O)₃SiC₃H₆SC₃H₆OCH₂CF(CF₃)[OCF₂CF(CF₃)]_(n)OC₄F₉O[(CF(CF₃)CF₂O]_(m)CF(CF₃)CH₂OC₃H₆SC₃H₆Si(OC₂H₅)₃-   C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂CH₂SC₃H₆Si(OCH₃)₃-   C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂CH₂SC₃H₆Si(OC₂H₅)₃-   C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CF₂OC₃H₆SC₃H₆Si(OCH₃)₃-   C₃F₇O[CF₂CF₂CF₂O]_(n)C₂F₄CH₂OC₃H₆SC₃H₆Si(OCH₃)₃, and-   C₃F₇O[CF₂CF₂CF₂O]_(n)C₂F₄CH₂CH₂SC₃H₆Si(OCH₃)₃.

The compounds of formula I can be synthesized using standard techniques.For example, a commercially available, or readily synthesized,mercaptosilane of the formula HS—R²—Si(Y)_(x)(R³)_(3-x), may be combinedwith an ethylenically unsaturated perfluoropolyether compound of theformula R_(f)—R¹—CH═CH₂, as shown in the following Scheme. Disilylcompounds of Formula I, where y is 2, may also be prepared by these samegeneral techniques.

whereR¹, R², R³, R_(f), Y and x are as previously defined for Formula I. Withrespect the addition reaction of Scheme 1, the sulfur may add to eithercarbon atom of the ethylenically unsaturated group in which case the—C₂H₄— group is of the structure —CH(CH₃)— or —CH₂CH₂—.

The addition of the mercaptosilane (III) to the ethylenicallyunsaturated compound (II) may be effected using free radical initiators.Useful free radical initiators include inorganic and organic peroxides,hydroperoxides, persulfates, azo compounds, redox systems (e.g., amixture of K₂S₂O₈ and Na₂S₂O₅), and free radical photoinitiators such asthose described by K. K. Dietliker in Chemistry & Technology of UV & EBFormulation for Coatings, Inks & Paints, Volume 3, pages 276-298, SITATechnology Ltd., London (1991). Representative examples include hydrogenperoxide, potassium persulfate, t-butyl hydroperoxide, benzoyl peroxide,t-butyl perbenzoate, cumene hydroperoxide,2,2′-azobis(2-methylbutyronitrile), (VAZO 67) andazobis(isobutyronitrile) (AIBN). The skilled artisan will recognize thatthe choice of initiator will depend upon the particular reactionconditions, e.g., choice of solvent.

Perfluoropolyether compounds having an ethylenically unsaturated group,e.g. formula II, may be prepared by means known in the art. For example,a perfluorinated dihydroalcohol of the general formula R_(f)—CH₂—OH(prepared by reduction of the corresponding perfluorinated acyl fluorideor ester), may be reacted with an omega-haloalkene, such as allylbromide.

Alternatively, a perfluorinated acyl fluoride may be reacted by fluorideion catalyzed addition to an omega-haloalkene.

Other ethylenically unsaturated perfluoropolyethers can be prepared bythe reaction of a perfluoropolyether iodide, by the reaction ofpoly(hexafluoropropylene oxide) with lithium iodide at 180° C.) withethylene using a free radical catalyst such as benzoyl peroxide at 65°C. in the absence of a solvent (described in J. L. Howell et al., J.Fluorine Chem., vol. 125, (2004), p. 1513). The obtained primary orsecondary iodide can then undergo dehydroiodination using, for examplesodium methoxide in methanol, to form the ethylenically unsaturatedperfluoropolyether precursor.

Perfluoropolyether compounds can be obtained by oligomerization ofhexafluoropropylene oxide (HFPO) which results in a perfluoropolyethercarbonyl fluoride. This carbonyl fluoride may be converted into an acid,acid salt, ester, amide or alcohol by reactions well known to thoseskilled in the art. The carbonyl fluoride or acid, ester or alcoholderived therefrom may then be reacted further to introduce the desiredgroups according to known procedures.

It will be evident to one skilled in the art that a mixture ofperfluoropolyethers according to formula (I) may be used to prepare thefluorinated polyether compound of the fluorochemical composition.Generally, the method of making the perfluoropolyether according toformula (I) for the present invention will result in a mixture ofperfluoropolyethers that have different molecular weights and are freeof (1) fluorinated polyether compounds having a perfluorinated polyethermoiety having a molecular weight of less than 750 g/mol and (2)fluorinated polyether compounds having a perfluoropolyether moietyhaving a molecular weight greater than 10,000 g/mol.

The use of perfluoropolyethers corresponding to molecular weightsgreater than about 10,000 g/mol can induce processing problems. Theseproblems are typically due to the fact that the higher molecular weightmaterials lead to insolubility concerns, as well as in difficulty inapplication methods such as CVD coating due to the low vapor pressure ofthese higher molecular weight compounds. Additionally, the presence ofhigher molecular weight fluorinated polyether derivatives may haveconsiderable impact on the efficiency of the separation process ofmaterials via fractionation.

The fluorochemical composition are desirably free of or substantiallyfree of perfluoropolyether moieties having a molecular weight of lessthan 750 g/mol and those moieties having a molecular weight greater than5000 g/mol. By the term “substantially free of” is meant that theparticular perfluoropolyether moieties outside the molecular weightrange are present in amounts of not more than 10% by weight, preferablynot more than 5% by weight and based on the total weight ofperfluoropolyether moieties in the composition. Compositions that arefree of or substantially free of these moieties are preferred because oftheir beneficial environmental properties and their processability inthe further reaction steps.

If it is desired to apply the compounds of Formula I by a vapordeposition method, the molecular weight of the perfluoropolyether moietyis preferably less than 10,000 g/mole, and more preferably 1000 to 5000g/mole.

Coatings derived from the perfluoropolyether silane of formula I may beapplied to various substrates, particularly hard substrates, to renderthem oil-, water-, and soil repellent. This coating can be extremelythin, e.g. 1 to 50 molecular layers, though in practice a useful coatingmay be thicker.

Although the inventors do not wish to be bound by theory, compounds ofthe above formula I are believed to undergo a condensation reaction withthe substrate surface to form a siloxane layer via hydrolysis ordisplacement of the hydrolysable “Y” groups of Formula I. In thiscontext, “siloxane” refers to —Si—O—Si— bonds to which are attachedR_(f) segments (i.e. perfluoropolyether segments as in Formula Iherein), bonded to the silicon atoms through organic linking groups(such as the R¹ and R² groups in formula I herein.

A coating prepared from the perfluoropolyether silane coatingcomposition that includes compounds of formula I includes theperfluoropolyether silanes per se, as well as siloxane derivativesresulting from bonding to the surface of a preselected substrate. Thecoatings can also include unreacted or uncondensed “Si—Y” groups. Thecomposition may further contain may also contain non-silane materialssuch as oligomeric perfluoropolyether monohydrides, starting materialsand perfluoropolyether alcohols and esters. Likewise, vapor depositedperfluoropolyether silanes may include the silanes of Formula I per se,as well as the siloxane derivatives resulting from reaction with thesubstrate surface.

In one embodiment, the invention provides a coating compositioncomprising the perfluoropolyether silanol, a solvent, and optionallywater and an acid. To achieve good durability for many substrates, suchas ceramics, the compositions of the present invention preferablyinclude water. Thus the present invention provides a method of coatingcomprising the steps of providing contacting a substrate with a coatingcomposition comprising the perfluoropolyether silane of Formula I and asolvent. The coating composition may further comprise water and an acid.In one embodiment the method comprises contacting a substrate with acoating composition comprising the silane of Formula I and a solvent,and subsequently contacting the substrate with an aqueous acid.

When present, the amount of water typically will be between 0.1 and 20%by weight, preferably between 0.5% by weight and 15% by weight, morepreferably between 1 and 10% by weight, relative to the weight of thesilane of Formula I.

In addition to water, the compositions of the invention may also includean organic or inorganic acid. Organic acids include acetic acid, citricacid, formic acid and the like; fluorinated organic acids, such asCF₃SO₃H, C₃F₇CO₂K or those which can be represented by the formula R_(f)²[—(L)_(a)—Z]_(b) (IV) wherein R_(f) ² represents a mono or divalentperfluoroalkyl or perfluoropolyether group, L represents an organicdivalent linking group, Z represents an acid group, such as carboxylic,sulfonic or phosphonic acid group; a is 0 or 1 and b is 1 or 2.

Examples of suitable R_(f) ² groups include those given above for R_(f).Examples of organic acids of formula (IV) includeC₃F₇O(CF(CF₃)CF₂)₁₀₋₃₀CF(CF₃)COOH, commercially available from DuPont orCF₃(CF₂)₂OCF(CF₃)COOH. Examples of inorganic acids include sulphuricacid, hydrochloric acid and the like. The acid will generally beincluded in the composition in an amount between about 0.01 and 10%,more preferably between 0.05 and 5% by weight, relative to the weight ofthe silane.

The acid may be formulated into the coating composition per se, orsubsequent to coating with the perfluoropolyether silane, the coatedsubstrate may be dipped in an acid solution to effect the formation of asiloxane layer.

A coating composition of the present invention for many substrates mayinclude one or more organic solvents. The organic solvent or blend oforganic solvents used must be capable of dissolving at least 0.01% byweight of the perfluoropolyether silane of formula I. Furthermore, thesolvent or mixture of solvents may have a solubility for water of atleast 0.1% by weight and a solubility for acid of at least 0.01% byweight. If the organic solvent or mixture of organic solvents do notmeet these criteria, it may not be possible to obtain a homogeneousmixture of the fluorinated silane, solvent(s), and optional water andacid. Although such non-homogeneous compositions could be used to treata substrate, the coating obtained therefrom will generally not have thedesired oil/water repellency and will not have sufficient durabilityproperties.

Suitable organic solvents, or mixtures of solvents can be selected fromalkanes, aromatic solvents; aliphatic alcohols, such as methanol,ethanol, isopropyl alcohol; ketones, such as acetone or methyl ethylketone; esters, such as ethyl acetate, methyl formate and ethers, suchas diisopropyl ether.

Fluorinated solvents may be used alone or in combination with theorganic solvents in order to improve solubility of theperfluoropolyether silane. Such fluorinated solvents will generally notbe suitable for use on their own because may not meet the requirementsof solubility for water and acid, if present. Normally theperfluoropolyether silane may be first coated from a fluorinatedsolvent, and then subsequently contacted with aqueous acid.

Examples of fluorinated solvents include fluorinated hydrocarbons, suchas perfluorohexane or perfluorooctane, available from 3M; partiallyfluorinated hydrocarbons, such as pentafluorobutane, available fromSolvay, or CF₃CFHCFHCF₂CF₃, available from DuPont; hydrofluoroethers,including alkyl perfluoroalkyl ether such as methyl perfluorobutyl etheror ethyl perfluorobutyl ether, available from 3M as Novec™ HFE 7100 andNovec™ HFE 7200, respectively. Various blends of these materials withorganic solvents can be used.

A particularly preferred substrate is an antireflective substrate.Antireflective (AR) surfaces are substrates prepared by vacuumdeposition or sputtering of metal oxide thin films on substrates made ofglass or plastic are useful in ophthalmic devices and display devices ofelectronic equipment. Such metal oxide films are relatively porous andconsist of clusters of particles forming a relatively rough profile.Such coatings help reduce glare and reflection. When they are used inophthalmic eyewear they reduce eyestrain. When they are conductivecoatings, they also help reduce static discharge and electromagneticemissions. Thus, one application for these coatings is to providecontrast enhancement and antireflective properties to improve thereadability of display devices, such as computer monitors.Antireflective substrates are described in U.S. Pat. No. 5,851,674incorporated by reference herein in its entirety.

Various antisoiling coatings for antireflective coatings are known. Forexample, U.S. Pat. No. 6,906,115 (Hanazawa et al.) and U.S. Pat. No.6,183,872 (Tanaka et al.) both describe silicon-containing organicfluoropolymers that may be applied to antireflective substrates, such asophthalmic lenses. However, it has been noted that such antisoilingcoatings deleteriously effect the grinding operations in ophthalmic lensmanufacture. U.S. Pub. Appln. No 2003/004937, assigned to EssilorInternational, notes that the adhesion at the interface pad/convexsurface is altered or compromised even for the most efficienthydrophobic and/or oil-repellent coatings. The same reference attemptsto overcome the problems inherent with these commercial coatings byproviding a temporary protective coating having a surface energy of atleast 15 mJoules/m², so that the lens may be secured during the grindingoperations without slippage.

In many embodiments, the present invention further overcomes the knowndeficiency of currently available coatings, in which antireflectivelenses may be coated with the perfluoropolyether silane of theinvention, and secured in the lens edge cutting/grinding apparatus,thereby obviating the need for temporary layers as described in U.S.Pub. Appln. No. 2003/0049370. Thus, the present invention provides amethod of edge cutting of ophthalmic lenses by providing an ophthalmiclens having an antireflective coating and a coating of theperfluoropolyether silane of Formula I thereon, comprising blocking thelens, and edge cutting the lens. The method may be done in the absenceof a temporary protective coating.

Sputtered metal oxide antireflective coatings are generally durable anduniform. Also, their optical properties are controllable, which makesthem very desirable. They also have very high surface energies andrefractive indices. However, the high surface energy of a sputteredmetal oxide surface makes it prone to contamination by organicimpurities (such as skin oils). The presence of surface contaminantsresults in a major degradation of antireflectivity properties of themetal oxide coatings. Furthermore, because of the high refractiveindices, surface contamination becomes extremely noticeable to theend-user.

The present invention provides an oil-, water-, and soil-repellentcoating on an antireflective surface that is relatively durable, andmore resistant to contamination, and overcomes the deficiencies of priorart coatings with respect to edge-grinding processes. The presentinvention provides in one embodiment a method and composition for use inpreparing an antireflective article comprising a substrate having anantireflective surface and an antisoiling coating of less than about 200Angstroms thick deposited thereon. The antisoiling coating comprises aperfluoropolyether siloxane film of a thickness that does notsubstantially change the antireflective characteristics of theantireflective article.

The overall coating thickness of the antisoiling coating is generallygreater than a monolayer (which is typically greater than about 15Angstroms thick). That is, an antisoiling coating of the presentinvention may be at least about 20 Angstroms thick, and preferably, atleast about 30 Angstroms thick. Generally, it is less than about 200Angstroms thick, and preferably, less than about 100 Angstroms thick.The coating material is typically present in an amount that does notsubstantially change the antireflective characteristics of theantireflective article, i.e. that the antireflectivity that is differentby less than about 0.5 percentage units from that of the same articlewithout the perfluoropolyether silane coating.

The optical articles produced by the method of the present inventioninclude a substrate, such as glass or an organic polymeric substrate,optionally having a primed surface on which is coated an optionaladhesion enhancing coating, an antireflective composition, and anantisoiling coating derived from the perfluoropolyether silane offormula I.

Suitable transparent substrates for antireflective articles includeglass and transparent thermoplastic materials such aspoly(meth)acrylate, polycarbonate, polythiourethanes, polystyrene,styrene copolymers, such as acrylonitrile-butadiene-styrene copolymerand acrylonitrile-styrene copolymer, cellulose esters, particularlycellulose acetate and cellulose acetate-butyrate copolymer, polyvinylchloride, polyolefins, such as polyethylene and polypropylene,polyimide, polyphenyleneoxide, and polyesters, particularly polyethyleneterephthalate. The term “poly(meth)acrylate” (or “acrylic”) includesmaterials commonly referred to as cast acrylic sheeting, stretchedacrylic, poly(methylmethacrylate) “PPMA,” poly(methacrylate),poly(acrylate), poly(methylmethacrylate-co-ethylacrylate), and the like.The substrate thickness can vary, however, for flexible organic films ittypically ranges from about 0.1 mm to about 1 mm. Additionally, theorganic polymeric substrate can be made by a variety of differentmethods. For example, the thermoplastic material can be extruded andthen cut to the desired dimension. It can be molded to form the desiredshape and dimensions. Also, it can be cell cast and subsequently heatedand stretched to form the organic polymeric substrate.

The substrate on which the antireflective coating is deposited mayinclude a primed surface. The primed surface can result from theapplication of a chemical primer layer, such as an acrylic layer, orfrom chemical etching, electronic beam irradiation, corona treatment,plasma etching, or coextrusion of adhesion promoting layers. Such primedsubstrates are commercially available. For example, a polyethyleneterephthalate substrate primed with an aqueous acrylate latex isavailable from Imperial Chemical Industries Films, Hopewell, N.C.

The substrate may also include an adhesion-enhancing coating to improveadhesion between the antireflective coating and the substrate. Suchcoatings are commercially available. The adhesion enhancing coating isparticularly desirable for use on flexible organic polymeric substrates.In addition to enhancing adhesion of the antireflective coating to aprimed or unprimed organic polymeric substrate, an adhesion enhancingcoating may also provide increased durability to an antireflectivecoating on a flexible organic polymeric substrate by improving thescratch resistance of the antireflective coating.

A wide variety of coating methods can be used to apply a composition ofthe present invention to any substrate, such as spray coating, knifecoating, spin coating, dip coating, meniscus coating, flow coating, rollcoating, and the like. A preferred coating method for application of aperfluoropolyether silane mixture of the present invention includesspray application. A substrate to be coated can typically be contactedwith the coating composition at room temperature (typically, about 20 to25° C.).

The coating composition can be applied to substrates that are preheatedat a temperature of for example between 60 and 150° C. This is ofparticular interest for industrial production, where e.g. ceramic tilescan be treated immediately after the baking oven at the end of theproduction line. Following application, the treated substrate can bedried and cured at ambient or elevated temperature, e.g. at 40 to 300°C. and for a time sufficient to dry. The process may also require apolishing step to remove excess material.

Where the substrate is an antireflective coating, such as in opticallenses, the perfluoropolyether silane may be deposited by vapordeposition techniques, in addition to solution coating techniques. Theconditions under which the perfluoropolyether silane is vaporized mayvary according to the structure and molecular weight of the antisoilingperfluoropolyether silane. In some embodiments of the invention, thevaporizing may take place at pressures less than about 0.01 torr, atpressures less than 10⁻⁴ torr or even 10⁻⁵ torr. In embodiments of theinvention, the vaporizing may take place at temperatures of at leastabout 100° C., or above 200° C., or above 300° C. Advantageously, it hasbeen found that the instant perfluoropolyether silanes may be vapordeposited at lower temperatures than other antisoiling coatings, such asthose disclosed in U.S. Pat. No. 6,991,826 (Pellerite et al.).

The vapor deposition method may reduce opportunities for contaminationof the antireflective article surface through additional handling andexposure to the environment, leading to correspondingly lower yieldlosses. Furthermore, as the antireflective coatings are generallyapplied by vapor deposition, it is more efficient to apply theperfluoropolyether silanes by the same process in the same vacuumchamber. Thus, the method of the present invention enables applicationof the antisoiling compositions to antireflective lenses underprocessing conditions similar to those used in the industry for otherapplications, at decreased capital equipment costs and with thenecessity of solvent usage eliminated.

In one embodiment, the vaporizing comprises placing theperfluoropolyether silane and the antireflective substrate into achamber, decreasing the pressure in the chamber, and heating theperfluoropolyether silane. The perfluoropolyether silane is typicallymaintained in a crucible, but in some embodiments, the silane is imbibedin a porous matrix, such as a ceramic pellet, and the pellet heated inthe vacuum chamber. In a preferred embodiment, the antireflectivesubstrate comprises an antireflective ophthalmic lens. Furthermore, theantireflective ophthalmic lens may comprise a polycarbonate resin and anantireflective coating on the surface of the polycarbonate resin.

The present invention also provides a method of depositing anperfluoropolyether silane on an antireflective-coated ophthalmic lenscomprising vaporizing an perfluoropolyether silane of Formula I anddepositing the perfluoropolyether silane onto an antireflective coatedophthalmic lens, wherein the perfluoropolyether silane is placed in afirst chamber and the antireflective coated ophthalmic lens is placed ina second chamber connected to the first chamber such that vaporizedperfluoropolyether silane from the first chamber can deposit on theantireflective coated ophthalmic lens in the second chamber. In anotheraspect of the invention, the second chamber may remain at ambienttemperature while the first chamber is heated.

The present invention also provides a method for depositing theperfluoropolyether silane onto an antireflective substrate that maycomprise placing the silane and the antireflective substrate into a samechamber, heating the perfluoropolyether silane, and lowering thepressure in the chamber. Under some conditions, with some substrates,the antireflective substrate and the perfluoropolyether silane may beheated to the same temperature.

In a further aspect, the present invention provides a method ofpreparing an antireflective article comprising depositing anantireflective layer onto the surface of a transparent substrate andvapor depositing the perfluoropolyether silane of Formula I onto thesurface of the antireflective wherein the average molecular weight ofthe perfluoropolyether moiety is about 750 to about 5000, preferably1000 to 3000 g/mole.

Other useful substrates include ceramics, glass, metal, natural andman-made stone, thermoplastic materials (such as poly(meth)acrylate,polycarbonate, polystyrene, styrene copolymers, such as styreneacrylonitrile copolymers, polyesters, polyethylene terephthalate),paints (such as those based on acrylic resins), powder coatings, (suchas polyurethane or hybrid powder coatings), and wood. Various articlescan be effectively treated with the perfluoropolyether solution of thepresent invention to provide a water and oil repellent coating thereon.Examples include ceramic tiles, bathtubs or toilets, glass showerpanels, construction glass, various parts of a vehicle (such as themirror or windscreen), glass, and ceramic or enamel pottery materials.

Suitable substrates that can be treated in with the perfluoropolyethersilane coating composition include substrates having a hard surfacepreferably with functional groups capable of reacting with theperfluoropolyether silane according to Formula (I). Preferably, suchreactivity of the surface of the substrate is provided by activehydrogen atoms. When such active hydrogen atoms are not present, thesubstrate may first be treated in a plasma containing oxygen or in acorona atmosphere to make it reactive to the perfluoropolyether silane.

Useful substrates include those siliceous substrates including ceramics,glazed ceramics, glass, concrete, mortar, grout and natural and man-madestone. Various articles can be effectively treated with theperfluoropolyether silane of the present invention to provide a waterand oil repellent coating thereon. Examples include ceramic tiles,bathtubs or toilets, glass shower panels, construction glass, variousparts of a vehicle (such as the mirror or windscreen), and ceramic orenamel pottery materials. Treatment of glass employed for ophthalmicpurposes, e.g., glass lenses, with the composition of the presentinvention is especially advantageous.

Treatment of the substrates results in rendering the treated surfacesless retentive of soil and more readily cleanable due to the oil andwater repellent nature of the treated surfaces. These desirableproperties are maintained despite extended exposure or use and repeatedcleanings because of the high degree of durability of the treatedsurface as can be obtained through the compositions of this invention.

The substrate may be cleaned prior to applying the compositions of theinvention so as to obtain optimum characteristics, particularlydurability. That is, the surface of the substrate to be coated should besubstantially free of organic contamination prior to coating. Cleaningtechniques depend on the type of substrate and include, for example, asolvent washing step with an organic solvent, such as acetone orethanol.

The coating composition is typically a relatively diluted solution,containing between 0.01 and 50 percent by weight of theperfluoropolyether silane, more preferably, between 0.03 and 3 percentby weight of the perfluoropolyether silane, and most preferably, between0.05 and 1.0 percent by weight of perfluoropolyether silane. The ratioof the solvents, and optional water and acid should be chosen so as toobtain a homogeneous mixture.

For ease of manufacturing and for reasons of cost, the coatingcompositions of the present invention will generally be prepared shortlybefore use by diluting a concentrate of the perfluoropolyether silane offormula (I). The concentrate will generally comprises a concentratedsolution of the perfluoropolyether silane of formula (I) in an organicsolvent without water and/or acid being present in such concentrate. Theconcentrate should be stable for several weeks, preferably at least 1month, more preferably at least 3 months. It has been found that theperfluoropolyether silane of formula (I) can be readily dissolved in anorganic solvent at high concentrations.

A wide variety of coating methods can be used to apply a composition ofthe present invention, such as spray coating, knife coating, spincoating, dip coating, meniscus coating, flow coating, roll coating, andthe like, in addition to the vapor deposition techniques previouslydescribed. One coating method for application of a perfluoropolyethersilane coating composition is spray application. Roll coating maycomprise feeding the coating composition to a doctor blade, transferringthe coating composition from the doctor blade to a gravure roll, andapplying the coating composition to the antireflective surface of thesubstrate from the gravure roll. It may further comprise the step ofcoating the antisoiling coating composition further comprises applying asoft roll to a surface opposing the surface of the substrate.

A substrate to be coated can typically be contacted with the coatingcomposition at room temperature (typically, about 25 to 200° C.).Alternatively, the mixture can be applied to substrates which arepreheated at a temperature of for example between 60° C. and 150° C.This is of particular interest for industrial production, where e.g.ceramic tiles can be treated immediately after the baking oven at theend of the production line. Following application, the treated substratecan be dried and cured at ambient or elevated temperature, e.g. at 40 to300° C. and for a time sufficient to dry. The process may also require apolishing step to remove excess material.

EXAMPLES

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention. These examplesare merely for illustrative purposes only and are not meant to belimiting on the scope of the appended claims.

All parts, percentages, ratios, etc. in the examples and the rest of thespecification are by weight, unless noted otherwise. Solvents and otherreagents used were obtained from Sigma-Aldrich Chemical Company, St.Louis, Mo. unless otherwise noted.

Test Methods

Nuclear Magnetic Resonance (NMR)

¹H and ¹⁹F NMR spectra were run on a Varian UNITY plus 400 Fouriertransform NMR spectrometer (available from Varian NMR Instruments, PaloAlto, Calif.).

Gas Chromatography/Mass Spectroscopy (GCMS)

GCMS samples were run on, for example, a Finnigan TSQ7000 massspectrometer (available from Thermo Electron Corporation, Waltham,Mass.).

Gas Chromatography (GC)

GC samples were run on a Hewlett Packard 6890 Series Gas Chromatograph,obtainable from Agilent Technologies, Palo Alto, Calif.

IR Spectroscopy (IR)

IR spectra were run on a Thermo-Nicolet, Avatar 370 FTIR, obtainablefrom Thermo Electron Corporation, Waltham, Mass.

Example 1 Preparation ofC₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂OC₃H₆SC₃H₆Si(OCH₃)₃

The intermediate alcohol was prepared as follows: Isopropyl alcohol (200grams) was placed in a 2 L three-necked round bottom flask equipped withan overhead stirrer, temperature sensor and addition funnel and cooledto <10° C. using a water/ice bath. Sodium borohydride (34 grams, 0.9mol) was added in several small portions.C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CO₂CH₃ (900 grams, M_(n)=1262, 0.71 mol)was added dropwise while stirring under nitrogen. The temperature wasmaintained between 0° C. and 10° C. The ester addition was completed inapproximately one hour. After the addition of the ester was complete,the reaction was continuously stirred while maintaining the temperaturebetween 0° C. and 10° C. The reaction mixture was then allowed to warmto room temperature and stirred overnight.

600 mL of a 20-wt % aqueous solution of ammonium chloride was addeddropwise to the thickened mixture at room temperature. On completeaddition, the temperature was kept below 45° C. using a cooling bath.After adding all of NH₄Cl solution, the mixture was stirred at roomtemperature for about 30 minutes, then the phases were allowed toseparate. The upper aqueous layer was removed and the lower alcoholphase was washed three times with 500 mL portions of deionized water.The residual solvent was removed by distillation under reduced pressureusing rotary evaporator at 60° C. to yield 884 grams of the intermediate(colorless oil).

The intermediate ether was prepared as follows:C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂OH (200 grams, M_(n)=1234, 0.16 mol) wasplaced in a 2 L three-necked round bottom flask equipped with a stirringbar, temperature sensor and condenser. Tert-Butyl alcohol (400 grams)was added, followed by potassium tert-butoxide (20 grams, 0.18 mol),added in small portions. The reaction mixture was heated to 40° C. undernitrogen. The mixture, which was initially cloudy, cleared to atransparent solution. Allyl bromide (21.6 grams, 0.18 mol) was added inone portion. The cloudy reaction mixture was then heated to 40° C. undernitrogen for 18 hours, then the reaction mixture containing undissolvedsalts was cooled to room temperature and diluted with 500 mL deionizedwater followed by 250 mL 2N HCl and 500 mL deionized water. The mixturewas stirred for 30 minutes and the layers were allowed to separate. Theaqueous phase was decanted. The organic phase was washed two additionaltimes with 1 L deionized water. 250 mL HFE-7100 (available undertrademark Novec™ HFE-7100 Fluid, from 3M Company, St. Paul, Minn.) wasadded to dissolve the product. The organic phase was separated fromremaining water in a separatory funnel and the excess HFE-7100 removedunder vacuum by rotary evaporation at 60° C. to yield 212 grams of acolorless oil of the product allyl ether:C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂OCH₂CH═CH₂.

The product allyl ether, (24 grams, 0.019 mole, M_(n)=1274, consistingof a mixture of oligomeric compounds with the value of n ranging fromabout 3 to about 8), HSC₃H₆Si(OCH₃)₃ (3.7 grams, 0.019 mol, obtainedfrom Alfa Aesar, Ward Hill, Mass.), ethyl acetate (60 g) and2,2′-azobis(2-methylpropionitrile) (Vazo™ 64, 0.12 grams, obtained fromDuPont de Nemours & Co., Wilmington, Del.) were combined in a 250 mLround bottom flask equipped with a thermocouple temperature probe,magnetic stir bar and a water filled condenser under a nitrogenatmosphere. The mixture was then degassed four times, heated to refluxand held at that temperature for 16 hours during which time the reactionsolution became completely homogeneous. The solution was cooled in a dryice/acetone bath which caused a phase separation. The upper ethylacetate phase was removed and the remaining lower phase extracted withFC72™ (perfluorohexane, obtained from 3M Company, St. Paul, Minn.), thelower fluorochemical phase separated from the residual ethyl acetate andsubsequently the FC72™ removed by rotary evaporation. The IR spectrum(Thermo-Nicolet, Avatar 370 FTIR, obtainable from Thermo ElectronCorporation, Waltham, Mass.) was consistent with the expected silane.

Example 2 Preparation ofC₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CO₂C₃H₆SC₃H₆Si(OCH₃)₂

Hexafluoropropylene oxide was oligomerized to give an acid fluoridemixture (C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)COF) essentially as described inU.S. Pat. No. 3,242,218 and fractionated to remove lower boiling pointoligomers as described in U.S. Pat. No. 6,923,921. Allyl alcohol (12.8grams, 0.22 mol) was added to the acid fluoride mixture (87 grams,M_(n)=1180) in one portion and the mixture stirred at room temperature(after the initial exotherm) for 18 hours. The reaction mixture wasdiluted with acetone and the lower insoluble fluorochemical phaseseparated and washed once more with an equal volume of acetone. Residualacetone in the fluorochemical phase was removed by rotary evaporation togive 81.1 grams oil. The IR spectrum showed the carbonyl band for theallyl ester at 1787.4 cm⁻¹. Analysis of the mixture by GC (HewlettPackard 6890 Series Gas Chromatograph, obtainable from AgilentTechnologies, Palo Alto, Calif.) showed that the starting acid fluoridecomponents were completely gone and a new series of peaks for the allylester (C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CO₂CH₂CH═CH₂) had appeared. Therewas approximately 8% of a series of oligomers in which the COF group wasreplaced by hydrogen and this material was used without furtherpurification in the next step.

C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CO₂CH₂CH═CH₂ (50 grams, 0.041 mol),HSC₃H₆Si(OCH₃)₃ (9.6 grams, 0.049 mol, obtained from Alfa Aesar, WardHill, Mass.), 2-butanone (60 grams) and2,2′-azobis(2-methylpropionitrile) (Vazo™ 64, 0.16 grams, obtained fromDuPont de Nemours & Co., Wilmington, Del.) were combined in a 250 mLround bottom flask equipped with a thermocouple temperature probe,magnetic stir bar and a water filled condenser under a nitrogenatmosphere. After degassing, the mixture was heated to 79° C. for 16hours, and then cooled to room temperature. FC72™ (about 50 mL) wasadded and the lower phase separated and washed one time with acetone toremove the excess mercaptosilane. The solvents were removed by rotaryevaporation to afford 50.1 grams of a light yellow oil. This product wasanalyzed by H-NMR (Varian UNITY plus 400 Fourier transform NMRspectrometer (available from Varian NMR Instruments, Palo Alto, Calif.)and found to be a mixture of 45% ester/silane and 40% starting materialallyl ester with about 15% of the corresponding hydride. The mixture wassubsequently treated with 20 grams more of the mercaptosilane underidentical reaction conditions to those described above to afford thefinal composition which was 81% desired silane, 0.6% starting allylester and 18% hydride.

Example 3 Preparation of(CH₃O)₃SiC₃H₆SC₃H₆OCH₂CF₂(OC₂F₄)n(OCF₂)nCF₂CH₂OC₃H₆SC₃H₆Si(OCH₃)₃

Fomblin™ ZDOL perfluoropolyether diol (157 grams, EW=950, obtained fromSolvay Solexis, Houston, Tex.), was dissolved in a mixture of HFE™ 7100(150 mL) and dimethoxyethane (100 mL, obtained from Sigma-Aldrich, St.Louis, Mo.) in a 1 L, 3-necked round bottom flask equipped with athermocouple, addition funnel and overhead stirrer. To this mixture,potassium hydroxide (14.0 grams, dissolved in 9 mL water) was added andthe mixture heated to between 40° C. and 50° C. and stirred for onehour. Tetrabutylammonium bromide (3.0 grams dissolved in 1 mL water) wasadded followed by the dropwise addition of allyl bromide (31 grams,obtained from Sigma-Aldrich, St. Louis, Mo.) over a period of about onehour. The reaction mixture was then stirred for 16 hours at 45° C. Adistillation head was attached and the solvents and water were distilleduntil the pot temperature reached about 120° C. The reaction mixture wasthen cooled, a vacuum of 0.02 atmospheres (15 mmHg) applied, and thetemperature was again raised to about 120° C. The mixture was held atthis temperature for about one hour. After cooling to room temperature,HFE™ 7100 (250 mL) was added and the mixture was filtered under vacuumthrough a sintered glass funnel to remove the solids. The solids werewashed with a further 75 mL of HFE™ 7100. The filtrate was washed onetime with 1% aqueous hydrochloric acid, the lower fluorochemical phaseseparated and the solvent removed by rotary evaporation to give 158grams of amber, clear liquid of the bis-allyl ether. The IR spectrumshowed that the alcohol band had completely disappeared.

The bis-allyl ether (35.8 grams, 0.017 mol), HSC₃H₆Si(OCH₃)₃ (13.5grams, 0.067 mol), ethyl acetate (100 grams) and2,2′-azobis(2-methylpropionitrile) (Vazo™ 64, 0.16 grams) were combinedin a 250 mL round bottom flask equipped with a thermocouple temperatureprobe, magnetic stir bar and a water filled condenser under a nitrogenatmosphere. After degassing as in Example 1, the mixture was heated to70° C. for 16 hours. The solvent was removed by rotary evaporation andthe excess mercaptosilane starting material removed by vacuumdistillation at 0.002 atmospheres (2 mm Hg) to yield 39.6 grams of thedesired product.

Example 4 Preparation of(CH₃O)₃SiC₃H₆SC₃H₆OCH₂CF(CF₃)[OCF₂CF(CF₃)]_(n)OC₄F₉O[(CF(CF₃)CF₂O]_(m)CF(CF₃)CH₂OC₃H₆SC₃H₆Si(OCH₃)₃

This silane was prepared as in Example 3, except with the followingcharges: Fluorochemical diol, prepared as in U.S. Pat. No. 3,574,770,hydroxyl EW=610: 100 grams; HFE™ 7100: 150 mL; dimethoxyethane: 100 mL;KOH: 14 grams dissolved in 9 mL water; tetrabutylammonium bromide: 3grams dissolved in 1 mL water; allyl bromide: 31 grams (0.26 mol). Thereaction conditions and the workup procedure were identical to Example 3to afford 92 grams of tan liquid of the desired bis (allyl) ether.

The bis (allyl) ether (20 grams, 0.015 mol) was combined withHSC₃H₆Si(OCH₃)₃ (14 g, 0.07 mol), ethyl acetate (40 grams) and2,2′-azobis(2-methylpropionitrile) (Vazo™ 64, 0.045 grams) in a 250 mLround bottom flask equipped with a thermocouple temperature probe,magnetic stir bar and a water filled condenser under a nitrogenatmosphere. After degassing, the mixture was heated to 70° C. for 16hours. The solvent was removed by rotary evaporation and the excessmercaptosilane removed by vacuum distillation at 0.002 atmospheres (2mmHg) to yield 25.6 grams of the desired product. The IR spectrum wasconsistent with the desired bis (silane).

Example 5 Preparation ofC₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂CH₂SC₃H₆Si(OCH₃)₃

C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH═CH₂ was prepared by reaction ofC₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂CH₂I with sodium methoxide in methanolat reflux. The iodide in turn was prepared by the reaction ofC₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)I with ethylene at 65° C. using benzoylperoxide as initiator. The vinyl compound (28.5 grams, 0.026 mol, about76% purity) was combined with HSC₃H₆Si(OCH₃)₃ (10.2 grams, 0.05 mol),2-butanone (about 60 grams) and 2,2′-azobis(2-methylpropionitrile)(Vazo™ 64, 0.1 grams) in a 250 mL round bottom flask equipped with athermocouple temperature probe, magnetic stir bar and a water filledcondenser under a nitrogen atmosphere. After degassing, the mixture washeated to 70° C. for 16 hours. The solvent was removed by rotaryevaporation and the residue taken up in perfluoropentane, PF 5050™(available as 3M™ Performance Fluid PF-5050 from 3M Company, St. Paul,Minn.) and washed with 2-butanone to remove the excess starting materialsilane and the solvent removed by rotary evaporation to afford 30.5grams silane.

Example 6 Preparation ofC₃F₇O[CF(CF₃)CF₂O)_(n)CF(CF₃)CF₂OC₃H₆SC₃H₆Si(OCH₃)₃

The intermediate C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CF₂OCH₂CH═CH₂ was preparedas follows: C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)COF (M_(n)=1180, prepared asdescribed in Example 2, 170 grams, 0.14 mol), anhydrous diglyme (354grams), potassium iodide (0.5 grams), potassium fluoride (12.8 grams,0.22 mol), Adogen™ 464 (9.3 grams of a solution of 49% by weight inanhydrous diglyme) and allyl bromide (54 grams, 0.44 mol) were combinedin a 1L three necked round bottom flask equipped with an overheadstirrer, condenser and thermocouple temperature probe and the mixtureheated to 75° C. with stirring under a nitrogen atmosphere for 72 hours.An additional 74 grams of allyl bromide was then added and the mixtureheated at 75° C. for an additional 72 hours. The composition of thereaction mixture at this time was about 44% starting material acidfluoride, 41% desired allyl ether and 10% allyl ester. The reactionmixture was filtered to remove the solids and phase separated from thediglyme solution. The fluorochemical phase was then washed with ethylacetate to remove the remaining organic solvents and reagents. Furtherpurification was effected by dilution of the fluorochemical phase withHFE™ 7100 followed by reaction with aqueous potassium hydroxide to aphenolphthalein endpoint. After phase separation (which was effected byfreezing the emulsified reaction mixture), the resulting fluorochemicalphase was distilled and the distillate used in the following procedure.The composition of the distillate was approximately 34% of the allylether and 57% C₃F₇O[CF(CF₃)CF₂O]_(n)CFHCF₃.

The allyl ether prepared as described above was treated withHSC₃H₆Si(OCH₃)₃ (14.0 grams) in 2-butanone solvent (125 mL) using AIBNinitiator (0.15 g) and degassed. This reaction mixture was heated to 70°C. for 16 hours. After cooling to room temperature, the reaction mixturewas treated with perfluoropentane to extract the product following bywashing of the perfluoropentane solution with 2-butanone to remove theexcess silane.

Treatments and Test Methods

Treatment of Ophthalmic Lenses by Dip Coat

A 0.1% solution of the selected fluorochemical silane in HFE-7100™ wasplaced in a glass container of the dip coater. The clean lens was dippedinto the solution at the speed of 15 mm/sec and allowed to staysubmerged for 2 seconds. Then the lens was withdrawn from the solutionat the speed of 15 mm/sec. The coated lens was dried for 30 minutes inair and then dipped into 0.1% HCl solution at a similar dipping andwithdrawal speed. Any excess acid was blown off with nitrogen gas. Thelens was placed in an aluminum pan and cured in the oven for 30 minutesat 60° C.

Treatment of Ophthalmic Lenses by Chemical Vapor Deposition (CVD)

A clean lens was treated with each of selected fluorochemical silanes ofthis invention as well as a comparative silane (ECC-1000™, Easy CleanCoating-1000™, (CH₃O)₃SiC₃H₆NHCOCF₂(OC₂F₄)n(OCF₂)nCF₂CONHC₃H₆Si(OCH₃)₃,obtained from 3M Company, St. Paul, Minn.) in a vapor deposition chamberunder 3×10⁻⁷ torr pressure. The vaporization temperature for the silanesranged from 350-500° C. as indicated in Table 1 below.

The CVD (chemical vapor deposition) experimental results reported inTable 1 show that the silanes of this invention, with the mercaptolinkage group, require lower vaporization temperatures for effectivedeposition. For example, the CVD process temperature for the silane ofExample 3,(CH₃O)₃SiC₃H₆SC₃H₆OCH₂CF₂(OC₂F₄)n(OCF₂)nCF₂CH₂OC₃H₆SC₃H₆Si(OCH₃)₃ isabout 50° C. lower than that for ECC-1000™ with a similarperfluoropolyether backbone but with a carboxamido linking group.

TABLE 1 Required CVD Vaporization Temperature for Silanes VaporizationSilane: Linkage group: Temperature (° C.): Example 1 Mercapto —S— 415Example 2 Mercapto —S— 415 Example 3 Mercapto —S— 415 Example 4 Mercapto—S— 415 Example 5 Mercapto —S— 415 ECC1000 Carboxamido —CONH— 475

Drain Time Test:

For this test the drain time of a liquid from a treated ophthalmic lenswas determined using a dip coater. The treated lenses are dipped intoand subsequently withdrawn from a liquid (either oleic acid orisopropanol (IPA)). The withdrawal speed for the test was 5 cm (2inches) per second. The time needed for the liquid to drain completelywas measured with a timer.

Table 2 summarizes the measured drain times for the CVD and dip coatedpolycarbonate lenses for isopropanol and oleic acid. According to thedata, in general, the CVD coating of the lenses resulted in shorterdrain times for both IPA and oleic acid than the dip coating. The dataalso indicate that independent of the coating method, the silanes with amercapto linking group result in shorter drain times than carboxamidolinking group even when they have similar fluorochemical chain (Example3 vs. ECC-1000^(FTM)).

TABLE 2 Drain time data for various silane treatments Oleic AcidIsopropanol Drain Time Drain Time Silane: Coating Method: (seconds):(seconds): Example 1 CVD 12 3 Example 1 Dip Coat 13 4 Example 2 CVD 11 4Example 2 Dip Coat 14 5 Example 3 CVD 11 3 Example 3 Dip Coat 10 4Example 4 CVD 19 14 Example 4 Dip Coat 17 18 Example 5 CVD 34 10 Example5 Dip Coat 17 4 ECC1000 CVD 15 9 ECC1000 Dip Coat 13 9 Crizal ™ CVD 2615 Alize ™ CVD 10 3 Comparative A Dip Coat 12 3 Comparative B Dip Coat21 41

-   -   Crizal™, Obtained from Essilor International, St. Petersburg,        Fla.    -   Alize™, Obtained from Essilor International, St. Petersburg,        Fla.

The silane of Comparative A has a formula ofC₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CONHC₃H₆Si(OCH₃)₃The silane of Comparative B is similar to the silane of Example 4 but iscarboxamidosilane.

Static and Dynamic Contact Angles:

The static, advancing and receding contact angle test provides a quickand precise prediction of the surface properties of coating materials.

The contact angles for treated lenses (after drying and curing) weremeasured using a Kruss G120 and AST VCA 2500 XE Video Contact AngleSystem (AST Products, Inc.), both equipped with a computer for controland date process. The data was generated for both water andn-hexadecane. Table 3 summarizes the static, advancing and recedingcontact angles for lenses treated with various silanes using both CVDand dip coating processes. Measured contact angles were high for alltreated lenses, although, in general, the lenses treated by dip coatingresulted in slightly higher contact angles. It was notable that thecontact angles for CVD coated lenses were very close to those for thedip coated lenses which indicated that the CVD coating were successfullyapplied.

TABLE 3 Contact angle data for various silane treatments StaticAdvancing Receding Coating Contact Angle Contact Angle Contact AngleSilane: Method: Water Hexadecane Water Hexadecane Water HexadecaneExample 1 CVD 114 70 117 72 81 62 Example 1 Dip Coat 117 78 121 79 10968 Example 2 CVD 104 65 107 68 65 54 Example 2 Dip Coat 115 72 121 77 9563 Example 3 CVD 107 65 110 67 81 57 Example 3 Dip Coat 109 67 112 69 8364 Example 4 CVD 109 66 114 68 80 56 Example 4 Dip Coat 107 93 112 67 7150 Example 5 CVD 98 60 101 61 72 47 Example 5 Dip Coat 115 73 122 75 8561 Crizal ™ CVD 118 77 127 78 91 57 Alize ™ CVD 108 65 110 67 89 58ECC-1000 CVD 108 65 111 70 68 54 ECC-1000 Dip Coat 116 73 123 72 94 60Comp. A Dip Coat 123 78 105.5 67 100 67 Comp. B Dip Coat 116.5 68 77.559.5 77 61

Hysteresis of Treated Lenses:

The difference between the maximum (advancing) and minimum (receding)contact angle values is called the contact angle hysteresis. A greatdeal of research has gone into analysis of the significance ofhysteresis: it has been used to help characterize surface heterogeneity,roughness and mobility. Briefly, for surfaces which are not homogeneous,there are domains on the surface which present barriers to the motion ofthe contact line. In case of chemical heterogeneity these domainsrepresent areas with different contact angles than the surroundingsurface. For example when wetting with water, hydrophobic domains willpin the motion of the contact line as the liquid advances thusincreasing the contact angles. When the water recedes the hydrophilicdomains will hold back the draining motion of the contact line thusdecreasing the contact angle. It is possible that the easy cleaningperformance of a coated surface is correlated to the contact anglehysteresis. The smaller the contact angle hysteresis, the better theperformance. The Table 4 lists the hysteresis of several treated lenses.

TABLE 4 Contact angle hysteresis for various silanes Coating HysteresisHysteresis Silane: Method: Water: Hexadecane: Crizal CVD 36 21 Alize CVD21 9 1 CVD 35 10 1 dip coat 13 11 2 CVD 42 13 2 dip coat 26 14 3 CVD 2810 3 dip coat 29 5 ECC-1000 CVD 42 16 ECC-1000 dip coat 28 12 4 CVD 3411 4 dip coat 41 17 5 CVD 29 14 5 dip coat 37 15

Durability Test:

The durability silane treatments on lenses were determined in thefollowing manner: The treated lenses were subjected to an abrasion testusing a Lens Eraser Abrasion Tester (obtained from Colts Laboratories,Inc., Clearwater, Fla.) and a 3M High Performance Cloth (Scotch-Brite™Microfiber Dusting Cloth, obtained from 3M Company, St. Paul, Minn.)under a 2.27 kg (5 lbs.) load for 500 cycles. Then the contact anglesfor the treated lenses following the abrasion test were measured againusing the method described above. Table 5 shows the contact angle dataof the treated lenses after the abrasion resistance test. A comparisonof the contact angle data for Example 3 before (Table 3) and after(Table 5) the abrasion test indicated that the Example 3 material hadexcellent durability.

TABLE 5 Contact angle data for various silane treatments after abrasiontest Advancing Receding Coating Contact Angle Contact Angle Silane:Method: Water Hexadecane Water Hexadecane Example 1 CVD 98 46 58 35Example 1 Dip Coat 104 60 64 43 Example 2 CVD 87 — 47 9 Example 2 DipCoat 93 52 49 25 Example 3 CVD 107 63 68 47 Example 3 Dip Coat 108 70 8460 Example 4 CVD 90 55 59 36 Example 4 Dip Coat 96 70 57 41 Example 5CVD 80 46 47 27 Example 5 Dip Coat 108 86 71 60 Crizal CVD 89 33 40 19Alize CVD 107 56 69 42 ECC-1000 CVD 111 68 79 56 ECC-1000 Dip Coat 12064 82 56 Comp. A Dip Coat 97 55.5 55 34 Comp. B Dip Coat 95 48 60 32.3

Adhesion and Edging Testing:

This test is run to determine the ability of a pad to hold a lens inposition in the edger during the cutting operation. Sealing paper fromone side of the Leap Pad III (obtained from 3M Company, St. Paul, Minn.)was peeled and applied to the center of the coated lens, which is firmlyaffixed in the torque tool with 30 cm (12¼″) bar. A block, the devicethat holds the lens in position while the lens rotates, was applied tothe other side of the Leap Pad III. The torque tool with pad and lenswas inserted into the edger (alignment of block flanges into blocker iscritical) and firmly pressed with 2.86 atmospheres (42 psi) pressure onthe pad. The tip of the torque tool was lined up with zero degree on thetorque scale, and a horizontal force of 0.45 kilogram (6 lbs) wasapplied using spring scale for one minute and the new position of torquetool on the torque scale was recorded as the degree from the zeroposition. If the torque degree is less than or equal to 5, it isconsidered to have adequate adhesion and ability to hold the lens in theedging process. The test results for the silane treatments of thisinvention along with Alize are shown in the Table 6. The torque degreefor Alize lens was >15, which requires a special temporary coating forthe edging process. The new silane treatments described in thisinvention all pass this torque test (<5) except for Example 3, which hadthe torque degree of 8. If the CVD coated lens of Example 3 was firstwashed with isopropanol before the torque test, the adhesion wasimproved and passed the test. Therefore, the silane treatments of thisinvention do not require a special temporary coating for the edgingprocess.

TABLE 6 Summary of adhesion and edge test data for silane treatments:Torque Degree Torque Degree Example before IPA wash after IPA wash 1 4 24 3 8 4 4 3 5 4 Alize >15

1. A perfluoropolyether silane of the formula:R_(f)[—R¹—C₂H₄—S—R²—Si(Y)_(x)(R³)_(3-x)]_(y), wherein R_(f) is a mono-or divalent perfluoropolyether group, R¹ is a covalent bond, —O—, or adivalent alkylene or arylene group, or combinations thereof, saidalkylene groups optionally containing one or more catenary oxygen atoms;R² is a divalent alkylene or arylene group, or combinations thereof,said alkylene groups optionally containing one or more catenary oxygenatoms; Y is a hydrolysable group, and R³ is a monovalent alkyl or arylgroup, x is 1, 2 or 3; and y is 1 or
 2. 2. The perfluoropolyether silaneof claim 1 wherein R_(f) is a perfluoropolyether group comprisingperfluorinated repeating units selected from the group consisting of—(C_(n)F_(2n))—, —(C_(n)F_(2n)O)—, —(CF(Z)O)—, —(CF(Z)C_(n)F_(2n)O)—,—(C_(n)F_(2n)CF(Z)O)—, —(CF₂CF(Z)O)—, and combinations thereof, whereinn is 1 to 4 and Z is a perfluoroalkyl group, a perfluoroalkoxy group, orperfluoroether group.
 3. The perfluoropolyether silane of claim 1,wherein Y is a halogen, a C₁-C₄ alkoxy group, or a C₁-C₄ acyloxy group.4. The perfluoropolyether silane of claim 1 wherein saidperfluoropolyether moiety has a molecular weight of at least 750 g/mole.5. The perfluoropolyether silane of claim 1 wherein saidperfluoropolyether moiety is selected from—CF₂O(CF₂O)_(m)(C₂F₄O)_(p)CF₂—, wherein an average value for m and p is0 to 50, with the proviso that m and p are not simultaneously 0;—CF₂O(C₂F₄O)_(p)CF₂—,—CF(CF₃)O—(CF₂CF(CF₃)O)_(p)—C₄F₈O—(CF(CF₃)CF₂O)_(p)—CF(CF₃)—, and—(CF₂)₃O(C₄F₈O)_(p)(CF₂)₃—, wherein an average value for p is 1 to 50.6. The perfluoropolyether silane of claim 1 wherein R_(f) is amonovalent perfluoropolyether group.
 7. The perfluoropolyether silane ofclaim 1 selected from the group consisting ofC₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂OC₃H₆SC₃H₆Si(OCH₃)₃C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂OC₃H₆SC₃H₆Si(OC₂H₅)₂C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CO₂C₃H₆SC₃H₆Si(OCH₃)₃C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CO₂C₃H₆SC₃H₆Si(OC₂H₅)₃(CH₃O)₃SiC₃H₆SC₃H₆OCH₂CF₂(OC₂F₄)_(n)(OCF₂)_(n)CF₂CH₂OC₃H₆SC₃H₆Si(OCH₃)₃(C₂H₅O)₃SiC₃H₆SC₃H₆OCH₂CF₂(OC₂F₄)_(n)(OCF₂)_(n)CF₂CH₂OC₃H₆SC₃H₆Si(OC₂H₅)₃(CH₃O)₃SiC₃H₆SC₃H₆OCH₂CF(CF₃)[OCF₂CF(CF₃)]_(n)OC₄F₉O[(CF(CF₃)CF₂O]_(m)CF(CF₃)CH₂OC₃H₆SC₃H₆Si(OCH₃)₃(C₂H₅O)₃SiC₃H₆SC₃H₆OCH₂CF(CF₃)[OCF₂CF(CF₃)]_(n)OC₄F₉O[(CF(CF₃)CF₂O]_(m)CF(CF₃)CH₂OC₃H₆SC₃H₆Si(OC₂H₅)₃C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂CH₂SC₃H₆Si(OCH₃)₃C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CH₂CH₂SC₃H₆Si(OC₂H₅)₃C₃F₇O[CF(CF₃)CF₂O]_(n)CF(CF₃)CF₂OC₃H₆SC₃H₆Si(OCH₃)₃C₃F₇O[CF₂CF₂CF₂O]_(n)C₂F₄CH₂OC₃H₆SC₃H₆Si(OCH₃)₃, andC₃F₇O[CF₂CF₂CF₂O]_(n)C₂F₄CH₂CH₂SC₃H₆Si(OCH₃)₃, wherein n is from 1 to 50and n+m is up to
 30. 8. A method of preparing the perfluoropolyethersilane of claim 1 comprising the free radical addition of amercaptosilane of the formula HS—R²—Si(Y)_(x)(R³)_(3-x), to anethylenically unsaturated fluorinated compound of the formula:R_(f)[—(R¹—CH═CH₂]_(y), wherein R_(f) is a mono- or divalentperfluoropolyether group, R¹ is a covalent bond, —O—, or a divalentalkylene or arylene group, or combinations thereof, said alkylene groupsoptionally containing one or more catenary oxygen atoms; R² is adivalent alkylene or arylene group, or combinations thereof, saidalkylene groups optionally containing one or more catenary oxygen atoms;R³ is a monovalent alkyl or aryl group, said alkylene groups, optionallycontaining one or more catenary oxygen atoms; Y is a hydrolysable group,and x is 1, 2 or 3, and y is 1 or
 2. 9. The method of claim 8 whereinthe free radical initiator is selected from inorganic and organicperoxides, hydroperoxides, persulfates, azo compounds, and redoxinitiators.
 10. A coated article comprising a substrate having a coatingof the perfluoropolyether silane of claim 1 on a surface thereof. 11.The coated article of claim 10 wherein the substrate is selected fromglass, ceramics, metal, stone, thermoplastic polymers, paints, powdercoatings, and wood.
 12. The coated article of claim 10 wherein thesubstrate has a siliceous surface.
 13. The coating article of claim 10wherein the substrate is an antireflective article.
 14. A coatingcomposition comprising the perfluoropolyether silane of claim 1, anorganic solvent, optionally an organic or inorganic acid, and optionallywater.
 15. A method of applying an antisoiling coating to a substrate,the method comprising applying a coating composition comprising at leastone perfluoropolyether silane of claim 1 and an organic solvent to atleast a portion of a surface of the substrate.
 16. The method of claim15 wherein the step of applying is selected from spray coating, knifecoating, spin coating, dip coating, meniscus coating, flow coating, androll coating.
 17. The method of claim 15 wherein said coatingcomposition further comprises water and an acid.
 18. The method of claim15 comprising the steps of applying the coating composition comprisingthe perfluoropolyether silane of claim 1, and an organic solvent, thencontacting the coated substrate with an aqueous acid.
 19. The method ofclaim 15 comprising between 0.01 and 50 percent by weight of theperfluoropolyether silane.
 20. The method of claim 15 further comprisingthe step of heating said coated substrate to temperatures of 40 to 300°C.